Probing equilibrium of molecular and deprotonated water on TiO2(110)

Zhi Tao Wang, Yang Gang Wang, Rentao Mu, Yeohoon Yoon, Arjun Dahal, Gregory K. Schenter, Vassiliki Alexandra Glezakou, Roger Rousseau, Igor Lyubinetsky, Zdenek Dohnálek

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

Understanding adsorbed water and its dissociation to surface hydroxyls on oxide surfaces is key to unraveling many physical and chemical processes, yet the barrier for its deprotonation has never been measured. In this study, we present direct evidence for water dissociation equilibrium on rutile-TiO2(110) by combining supersonic molecular beam, scanning tunneling microscopy (STM), and ab initio molecular dynamics. We measure the deprotonation/protonation barriers of 0.36 eV and find that molecularly bound water is preferred over the surface-bound hydroxyls by only 0.035 eV. We demonstrate that long-range electrostatic fields emanating from the oxide lead to steering and reorientation of the molecules approaching the surface, activating the O-H bonds and inducing deprotonation. The developed methodology for studying metastable reaction intermediates prepared with a high-energy molecular beam in the STM can be readily extended to other systems to clarify a wide range of important bond activation processes.

Original languageEnglish
Pages (from-to)1801-1805
Number of pages5
JournalProceedings of the National Academy of Sciences of the United States of America
Volume114
Issue number8
DOIs
Publication statusPublished - Feb 21 2017

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water
molecular beams
scanning tunneling microscopy
dissociation
lead oxides
reaction intermediates
rutile
retraining
activation
methodology
molecular dynamics
oxides
electric fields
molecules
energy

Keywords

  • Adsorbate dynamics
  • Dissociative adsorption
  • Kinetic barriers
  • Titanium dioxide
  • Water

ASJC Scopus subject areas

  • General

Cite this

Probing equilibrium of molecular and deprotonated water on TiO2(110). / Wang, Zhi Tao; Wang, Yang Gang; Mu, Rentao; Yoon, Yeohoon; Dahal, Arjun; Schenter, Gregory K.; Glezakou, Vassiliki Alexandra; Rousseau, Roger; Lyubinetsky, Igor; Dohnálek, Zdenek.

In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 114, No. 8, 21.02.2017, p. 1801-1805.

Research output: Contribution to journalArticle

Wang, ZT, Wang, YG, Mu, R, Yoon, Y, Dahal, A, Schenter, GK, Glezakou, VA, Rousseau, R, Lyubinetsky, I & Dohnálek, Z 2017, 'Probing equilibrium of molecular and deprotonated water on TiO2(110)', Proceedings of the National Academy of Sciences of the United States of America, vol. 114, no. 8, pp. 1801-1805. https://doi.org/10.1073/pnas.1613756114
Wang, Zhi Tao ; Wang, Yang Gang ; Mu, Rentao ; Yoon, Yeohoon ; Dahal, Arjun ; Schenter, Gregory K. ; Glezakou, Vassiliki Alexandra ; Rousseau, Roger ; Lyubinetsky, Igor ; Dohnálek, Zdenek. / Probing equilibrium of molecular and deprotonated water on TiO2(110). In: Proceedings of the National Academy of Sciences of the United States of America. 2017 ; Vol. 114, No. 8. pp. 1801-1805.
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AU - Schenter, Gregory K.

AU - Glezakou, Vassiliki Alexandra

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AB - Understanding adsorbed water and its dissociation to surface hydroxyls on oxide surfaces is key to unraveling many physical and chemical processes, yet the barrier for its deprotonation has never been measured. In this study, we present direct evidence for water dissociation equilibrium on rutile-TiO2(110) by combining supersonic molecular beam, scanning tunneling microscopy (STM), and ab initio molecular dynamics. We measure the deprotonation/protonation barriers of 0.36 eV and find that molecularly bound water is preferred over the surface-bound hydroxyls by only 0.035 eV. We demonstrate that long-range electrostatic fields emanating from the oxide lead to steering and reorientation of the molecules approaching the surface, activating the O-H bonds and inducing deprotonation. The developed methodology for studying metastable reaction intermediates prepared with a high-energy molecular beam in the STM can be readily extended to other systems to clarify a wide range of important bond activation processes.

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